The Spectrophotometry of Sodium Nitrite Solutions in Aqueous Sulphuric and Perchloric Acids and the Equilibrium between Nitrosonium Ion and Nitrous Acid

Abstract

The spectra of solutions of sodium nitrite in aqueous solutions of sulphuric and perchloric acids have been measured at a number of temperatures, and from these spectra the concentrations of the species HNO₂ and NO⁺ have been calculated over the acid-concentration ranges 0-100% sulphuric acid (by wt.) and 0-72% perchloric acid (by wt.). The changes due to temperature were found to be less than the experimental error in the determination of the concentrations of nitrous acid and nitrosonium ion. The equilibria of importance in such systems are discussed and equilibrium constants have been calculated for the reactions H₂SO₄ + HNO₂ <=> H₂O + NO⁺ + HSO₄^- and HClO₄ + HNO₂ H₂O + NO⁺ + ClO₄^- Attempts have been made to correlate the determined values for the concentration of nitrous acid and nitrosonium ion with the acidity functions J₀, C₀, and H_r for both solvent systems. The nitroacidium ion (H2NO₂⁺) in these systems is found to be less important than previously thought.'